Synergistic Effect and Fluorination Effect in Ethylene Polymerization by Nickel Phenoxyiminato Catalysts

Di Xu; Xiang-Xiang Zhao; Zhong-Tao Chen; Yu-Guo Ma

doi:10.1007/s10118-018-2081-3

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Synergistic Effect and Fluorination Effect in Ethylene Polymerization by Nickel Phenoxyiminato Catalysts

Articles | Updated：2021-02-18

- Synergistic Effect and Fluorination Effect in Ethylene Polymerization by Nickel Phenoxyiminato Catalysts
- Synergistic Effect and Fluorination Effect in Ethylene Polymerization by Nickel Phenoxyiminato Catalysts
- Chinese Journal of Polymer Science 2018年36卷第2期页码：244-251
- Affiliations：
  
  Beijing National Laboratory for Molecular Sciences(BNLMS), Center for Soft Matter Science and Engineering, Key Lab of Polymer Chemistry & Physics of Ministry of Education, College of Chemistry, Peking University, Beijing 100871, China
- Author bio：
  
  Yu-Guo Ma, E-mail ygma@pku.edu.cn
- Funds：
- DOI：10.1007/s10118-018-2081-3
  中图分类号：
- 收稿：2017-09-30，
  
  录用：2017-10-30，
  
  网络首发：2017-11-24，
  
  纸质出版：2018-02-05
- Accepted：
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Di Xu, Xiang-Xiang Zhao, Zhong-Tao Chen, 等. Synergistic Effect and Fluorination Effect in Ethylene Polymerization by Nickel Phenoxyiminato Catalysts[J]. Chinese Journal of Polymer Science, 2018,36(2):244-251.

Di Xu, Xiang-Xiang Zhao, Zhong-Tao Chen, et al. Synergistic Effect and Fluorination Effect in Ethylene Polymerization by Nickel Phenoxyiminato Catalysts[J]. Chinese Journal of Polymer Science, 2018, 36(2): 244-251.
Di Xu, Xiang-Xiang Zhao, Zhong-Tao Chen, 等. Synergistic Effect and Fluorination Effect in Ethylene Polymerization by Nickel Phenoxyiminato Catalysts[J]. Chinese Journal of Polymer Science, 2018,36(2):244-251. DOI： 10.1007/s10118-018-2081-3.

Di Xu, Xiang-Xiang Zhao, Zhong-Tao Chen, et al. Synergistic Effect and Fluorination Effect in Ethylene Polymerization by Nickel Phenoxyiminato Catalysts[J]. Chinese Journal of Polymer Science, 2018, 36(2): 244-251. DOI： 10.1007/s10118-018-2081-3.

摘要

Abstract

A series of binuclear nickel phenoxyiminato catalysts with different linkers and fluorine substituents were efficiently synthesized. Binuclear nickel catalysts with rigid linkers showed higher catalytic activity and thermal stability in ethylene polymerization and produced polymers with higher molecular weight possibly due to the larger steric hindrance and metal-metal synergistic effect. The introduction of fluorine atoms on the

-terphenyl moity also enhanced polymerization activity and molecular weight of polymer due to the electronic effect of fluorine atoms.

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references

T. R. Younkin , E. F. Connor , J. I. Henderson , S. K. Friedrich , R. H. Grubbs , D. A. Bansleben . Neutral, single-component nickel(Ⅱ) polyolefin catalysts that tolerate heteroatoms . Science , 2000 . 287 ( 5452 ): 460 - 462 . DOI: 10.1126/science.287.5452.460 http://doi.org/10.1126/science.287.5452.460 .

S. D. Ittel , L. K. Johnson , M. Brookhart . Late-metal catalysts for ethylene homo-and copolymerization . Chem. Rev. , 2000 . 100 ( 4 ): 1169 - 1204 . DOI: 10.1021/cr9804644 http://doi.org/10.1021/cr9804644 .

A. Nakamura , S. Ito , K. Nozaki . Coordination-insertion copolymerization of fundamental polar monomers . Chem. Rev. , 2009 . 109 ( 11 ): 5215 - 5244 . DOI: 10.1021/cr900079r http://doi.org/10.1021/cr900079r .

A. Nakamura , T. M. J. Anselment , J. Claverie , B. Goodall , R. F. Jordan , S. Mecking , B. Rieger , A. Sen , P. W. N. M. van Leeuwen , K. Nozaki . Ortho-phosphinobenzenesulfonate:a superb ligand for palladium-catalyzed coordination-insertion copolymerization of polar vinyl monomers . Acc. Chem. Res. , 2013 . 46 ( 7 ): 1438 - 1449 . DOI: 10.1021/ar300256h http://doi.org/10.1021/ar300256h .

L. K. Johnson , S. Mecking , M. Brookhart . Copolymerization of ethylene and propylene with functionalized vinyl monomers by palladium(Ⅱ) catalysts . J. Am. Chem. Soc. , 1996 . 118 ( 1 ): 267 - 268 . DOI: 10.1021/ja953247i http://doi.org/10.1021/ja953247i .

H. Mu , L. Pan , D. Song , Y. Li . Neutral nickel catalysts for olefin homo-and copolymerization:Relationships between catalyst structures and catalytic properties . Chem. Rev. , 2015 . 115 ( 22 ): 12091 - 12137 . DOI: 10.1021/cr500370f http://doi.org/10.1021/cr500370f .

L. Guo , S. Dai , X. Sui , C. Chen . Palladium and nickel catalyzed chain walking olefin polymerization and copolymerization . ACS Catal. , 2016 . 6 ( 1 ): 428 - 441 . DOI: 10.1021/acscatal.5b02426 http://doi.org/10.1021/acscatal.5b02426 .

T. Vaidya , K. Klimovica , A. M. LaPointe , I. Keresztes , E. B. Lobkovsky , O. Daugulis , G. W. Coates . Secondary alkene insertion and precision chain-walking:a new route to semicrystalline "polyethylene" from α-olefins by combining two rare catalytic events . J. Am. Chem. Soc. , 2014 . 136 ( 20 ): 7213 - 7216 . DOI: 10.1021/ja502130w http://doi.org/10.1021/ja502130w .

A. E. Cherian , J. M. Rose , E. B. Lobkovsky , G.W. Coates . A C2-symmetric, living α-diimine Ni(Ⅱ) catalyst:regioblock copolymers from propylene . J. Am. Chem. Soc. , 2005 . 127 ( 40 ): 13770 - 13771 . DOI: 10.1021/ja0540021 http://doi.org/10.1021/ja0540021 .

E. F. McCord , S. J. McLain , L. T. J. Nelson , S. D. Ittel , D. Tempel , C. M. Killian , L. K. Johnson , M. Brookhart . 13 C-NMR analysis of α-olefin enchainment in poly(α-olefins) produced with nickel and palladium α-diimine catalysts . Macromolecules , 2007 . 40 ( 3 ): 410 - 420 . DOI: 10.1021/ma061547m http://doi.org/10.1021/ma061547m .

L. Guo , C. Chen . (α-diimine)palladium catalyzed ethylene polymerization and (co)polymerization with polar comonomers . Sci. China Chem. , 2015 . 58 ( 11 ): 1663 - 1673 . DOI: 10.1007/s11426-015-5433-7 http://doi.org/10.1007/s11426-015-5433-7 .

Z. Guan , P. M. Cotts , E. F. McCord , S. J. McLain . Chain walking:a new strategy to control polymer topology . Science , 1999 . 283 ( 5410 ): 2059 - 2062 . DOI: 10.1126/science.283.5410.2059 http://doi.org/10.1126/science.283.5410.2059 .

M. A. Zuideveld , P. Wehrmann , C. Röhr , S. Mecking . Remote substituents controlling catalytic polymerization by very active and robust neutral nickel(Ⅱ) complexes . Angew. Chem. Int. Ed. , 2004 . 43 ( 7 ): 869 - 873 . DOI: 10.1002/(ISSN)1521-3773 http://doi.org/10.1002/(ISSN)1521-3773 .

H. L. Mu , W. P. Ye , D. P. Song , Y. S. Li . Highly active single-component neutral nickel ethylene polymerization catalysts:The influence of electronic effects and spectator ligands . Organometallics , 2010 . 29 ( 23 ): 6282 - 6290 . DOI: 10.1021/om100658j http://doi.org/10.1021/om100658j .

X. Hu , S. Dai , C. Chen . Ethylene polymerization by salicylaldimine nickel(Ⅱ) complexes containing a dibenzhydryl moiety . Dalton Trans. , 2016 . 45 ( 4 ): 1496 - 1503 . DOI: 10.1039/C5DT04408A http://doi.org/10.1039/C5DT04408A .

J. L. Rhinehart , L. A. Brown , B. K. Long . A robust Ni(Ⅱ) α-diimine catalyst for high temperature ethylene polymerization . J. Am. Chem. Soc. , 2013 . 135 ( 44 ): 16316 - 16319 . DOI: 10.1021/ja408905t http://doi.org/10.1021/ja408905t .

S. Dai , S. Zhou , W. Zhang , C. Chen . Systematic investigations of ligand steric effects on α-diimine palladium catalyzed olefin polymerization and copolymerization . Macromolecules , 2016 . 49 ( 23 ): 8855 - 8862 . DOI: 10.1021/acs.macromol.6b02104 http://doi.org/10.1021/acs.macromol.6b02104 .

S. Dai , C. Chen . Direct synthesis of functionalized high-molecular-weight polyethylene by copolymerization of ethylene with polar monomers . Angew. Chem. Int. Ed. , 2016 . 55 ( 42 ): 13281 - 13285 . DOI: 10.1002/anie.201607152 http://doi.org/10.1002/anie.201607152 .

P. Kenyon , S. Mecking . Pentafluorosulfanyl substituents in polymerization catalysis . J. Am. Chem. Soc. , 2017 . 139 ( 39 ): 13786 - 13790 . DOI: 10.1021/jacs.7b06745 http://doi.org/10.1021/jacs.7b06745 .

M. Chen , C. Chen . Rational design of high-performance phosphine sulfonate nickel catalysts for ethylene polymerization and copolymerization with polar monomers . ACS Catal. , 2017 . 7 ( 2 ): 1308 - 1312 . DOI: 10.1021/acscatal.6b03394 http://doi.org/10.1021/acscatal.6b03394 .

S. Dai , X. Sui , C. Chen . Highly robust palladium(Ⅱ) α-diimine catalysts for slow-chain-walking polymerization of ethylene and copolymerization with methyl acrylate . Angew. Chem. Int. Ed. , 2015 . 54 ( 34 ): 9948 - 9953 . DOI: 10.1002/anie.201503708 http://doi.org/10.1002/anie.201503708 .

M. P. Weberski , C. Chen , M. Delferro , C. Zuccaccia , A. Macchioni , T. J. Marks . Suppression of β-hydride chain transfer in nickel(Ⅱ)-catalyzed ethylene polymerization via weak fluorocarbon ligand-product interactions . Organometallics , 2012 . 31 ( 9 ): 3773 - 3789 . DOI: 10.1021/om3002735 http://doi.org/10.1021/om3002735 .

C. S. Popeney , A. L. Rheingold , Z. Guan . Nickel(Ⅱ) and palladium(Ⅱ) polymerization catalysts bearing a fluorinated cyclophane ligand:stabilization of the reactive intermediate . Organometallics , 2009 . 28 ( 15 ): 4452 - 4463 . DOI: 10.1021/om900302r http://doi.org/10.1021/om900302r .

J. Wang , E. Yao , Z. Chen , Y. Ma . Fluorinated nickel(Ⅱ) phenoxyiminato catalysts:exploring the role of fluorine atoms in controlling polyethylene productivities and microstructures . Macromolecules , 2015 . 48 ( 16 ): 5504 - 5510 . DOI: 10.1021/acs.macromol.5b01090 http://doi.org/10.1021/acs.macromol.5b01090 .

M. Chen , B. Yang , C. Chen . Redox-controlled olefin (co)polymerization catalyzed by ferrocene-bridged phosphine-sulfonate palladium complexes . Angew. Chem. Int. Ed. , 2015 . 54 ( 51 ): 15520 - 15524 . DOI: 10.1002/anie.201507274 http://doi.org/10.1002/anie.201507274 .

M. Zhao , C. Chen . Accessing multiple catalytically active states in redox-controlled olefin polymerization . ACS Catal. , 2017 . 7 ( 11 ): 7490 - 7494 . DOI: 10.1021/acscatal.7b02564 http://doi.org/10.1021/acscatal.7b02564 .

M. Li , X. Wang , Y. Luo , C. Chen . A second-coordination-sphere strategy to modulate nickel-and palladium-catalyzed olefin polymerization and copolymerization . Angew. Chem. Int. Ed. , 2017 . 56 ( 38 ): 11604 - 11609 . DOI: 10.1002/anie.v56.38 http://doi.org/10.1002/anie.v56.38 .

D. Zhang , C. Chen . Influence of polyethylene glycol unit on palladium-and nickel-catalyzed ethylene polymerization and copolymerization . Angew. Chem. Int. Ed. , 2017 . DOI: 10.1002/anie.201708212 http://doi.org/10.1002/anie.201708212 .

C. J. Stephenson , J. P. McInnis , C. Chen , M. P. Weberski , A. Motta , M. Delferro , T. J. Marks . Ni(Ⅱ) phenoxyiminato olefin polymerization catalysis:Striking coordinative modulation of hyperbranched polymer microstructure and stability by a proximate sulfonyl group . ACS Catal. , 2014 . 4 ( 3 ): 999 - 1003 . DOI: 10.1021/cs500114b http://doi.org/10.1021/cs500114b .

B. S. Xin , N. Sato , A. Tanna , Y. Oishi , Y. Konishi , F. Shimizu . Nickel catalyzed copolymerization of ethylene and alkyl acrylates . J. Am. Chem. Soc. , 2017 . 139 ( 10 ): 3611 - 3614 . DOI: 10.1021/jacs.6b13051 http://doi.org/10.1021/jacs.6b13051 .

J. P. McInnis , M. Delferro , T. J. Marks . Multinuclear group 4 catalysis:Olefin polymerization pathways modified by strong metal-metal cooperative effects . Acc. Chem. Res. , 2014 . 47 ( 8 ): 2545 - 2557 . DOI: 10.1021/ar5001633 http://doi.org/10.1021/ar5001633 .

Z. Chen , E. Yao , J. Wang , X. Gong , Y. Ma . Ethylene (co)polymerization by binuclear nickel phenoxyiminato catalysts with cofacial orientation . Macromolecules , 2016 . 49 ( 23 ): 8848 - 8854 . DOI: 10.1021/acs.macromol.6b02078 http://doi.org/10.1021/acs.macromol.6b02078 .

L. K. Johnson , C. M. Killian , M. Brookhart . New Pd(Ⅱ)-and Ni(Ⅱ)-based catalysts for polymerization of ethylene and α-olefins . J. Am. Chem. Soc. , 1995 . 117 ( 23 ): 6414 - 6415 . DOI: 10.1021/ja00128a054 http://doi.org/10.1021/ja00128a054 .

C. Popeney , Z. Guan . Ligand electronic effects on late transition metal polymerization catalysts . Organometallics , 2005 . 24 ( 6 ): 1145 - 1155 . DOI: 10.1021/om048988j http://doi.org/10.1021/om048988j .

C. S. Popeney , Z. Guan . Effect of ligand electronics on the stability and chain transfer rates of substituted Pd(Ⅱ) α-diimine catalysts . Macromolecules , 2010 . 43 ( 9 ): 4091 - 4097 . DOI: 10.1021/ma100220n http://doi.org/10.1021/ma100220n .

A. Osichow , I. Göttker-Schnetmann , S. Mecking . Role of electron-withdrawing remote substituents in neutral nickel(Ⅱ) polymerization catalysts . Organometallics , 2013 . 32 ( 18 ): 5239 - 5242 . DOI: 10.1021/om400757f http://doi.org/10.1021/om400757f .

I. Göttker-Schnetmann , P. Wehrmann , C. Röhr , S. Mecking . Substituent effects in (κ2-N, O)-salicylaldiminato nickel(Ⅱ)-methyl pyridine polymerization catalysts:terphenyls controlling polyethylene microstructures . Organometallics , 2007 . 26 ( 9 ): 2348 - 2362 . DOI: 10.1021/om0611498 http://doi.org/10.1021/om0611498 .

A. Bastero , I. Göttker-Schnetmann , C. Röhr , S. Mecking . Polymer microstructure control in catalytic polymerization exclusively by electronic effects of remote substituents . Adv. Synth. Catal. , 2007 . 349 ( 14-15 ): 2307 - 2316 . DOI: 10.1002/(ISSN)1615-4169 http://doi.org/10.1002/(ISSN)1615-4169 .

J. Saito , M. Mitani , J. Mohri , Y. Yoshida , S. Matsui , S. Ishii , S. Kojoh , N. Kashiwa , T. Fujita . Living polymerization of ethylene with a titanium complex containing two phenoxy-imine chelate ligands . Angew. Chem. Int. Ed. , 2001 . 40 ( 15 ): 2918 - 2920 . DOI: 10.1002/(ISSN)1521-3773 http://doi.org/10.1002/(ISSN)1521-3773 .

M. Mitani , J.-i. Mohri , Y. Yoshida , J. Saito , S. Ishii , K. Tsuru , S. Matsui , R. Furuyama , T. Nakano , H. Tanaka , S.-i. Kojoh , T. Matsugi , N. Kashiwa , T. Fujita . Living polymerization of ethylene catalyzed by titanium complexes having fluorine-containing phenoxy-imine chelate ligands . J. Am. Chem. Soc. , 2002 . 124 ( 13 ): 3327 - 3336 . DOI: 10.1021/ja0117581 http://doi.org/10.1021/ja0117581 .

M. Mitani , R. Furuyama , J.-i. Mohri , J. Saito , S. Ishii , H. Terao , T. Nakano , H. Tanaka , T. Fujita . Syndiospecific living propylene polymerization catalyzed by titanium complexes having fluorine-containing phenoxy-imine chelate ligands . J. Am. Chem. Soc. , 2003 . 125 ( 14 ): 4293 - 4305 . DOI: 10.1021/ja029560j http://doi.org/10.1021/ja029560j .

S.-i. Ishii , J. Saito , M. Mitani , J.-i. Mohri , N. Matsukawa , Y. Tohi , S. Matsui , N. Kashiwa , T. Fujita . Highly active ethylene polymerization catalysts based on titanium complexes having two phenoxy-imine chelate ligands . J. Mol. Catal. A:Chem. , 2002 . 179 ( 1 ): 11 - 16 . https://www.sciencedirect.com/science/article/pii/S138111690100303X https://www.sciencedirect.com/science/article/pii/S138111690100303X , .

J. Tian , P. D. Hustad , G. W. Coates . A new catalyst for highly syndiospecific living olefin polymerization:homopolymers and block copolymers from ethylene and propylene . J. Am. Chem. Soc. , 2001 . 123 ( 21 ): 5134 - 5135 . DOI: 10.1021/ja0157189 http://doi.org/10.1021/ja0157189 .

H. Makio , T. Fujita . Development and application of FI catalysts for olefin polymerization:unique catalysis and distinctive polymer formation . Acc. Chem. Res. , 2009 . 42 ( 10 ): 1532 - 1544 . DOI: 10.1021/ar900030a http://doi.org/10.1021/ar900030a .

M. Delferro , T. J. Marks . Multinuclear olefin polymerization catalysts . Chem. Rev. , 2011 . 111 ( 3 ): 2450 - 2485 . DOI: 10.1021/cr1003634 http://doi.org/10.1021/cr1003634 .

A. Motta , I. L. Fragalà , T. J. Marks . Proximity and cooperativity effects in binuclear d0 olefin polymerization catalysis. Theoretical analysis of structure and reaction mechanism . J. Am. Chem. Soc. , 2009 . 131 ( 11 ): 3974 - 3984 . https://iwe.pure.elsevier.com/en/publications/proximity-and-cooperativity-effects-in-binuclear-d-sup0sup-olefin https://iwe.pure.elsevier.com/en/publications/proximity-and-cooperativity-effects-in-binuclear-d-sup0sup-olefin , .

S. Sujith , D. J. Joe , S. J. Na , Y. W. Park , C. H. Choi , B. Y. Lee . Ethylene/polar norbornene copolymerizations by bimetallic salicylaldimine-nickel catalysts . Macromolecules , 2005 . 38 ( 24 ): 10027 - 10033 . DOI: 10.1021/ma051344i http://doi.org/10.1021/ma051344i .

Q. Chen , J. Yu , J. Huang . Arene-bridged salicylaldimine-based binuclear neutral nickel(Ⅱ) complexes:Synthesis and ethylene polymerization activities . Organometallics , 2007 . 26 ( 3 ): 617 - 625 . DOI: 10.1021/om060778e http://doi.org/10.1021/om060778e .

M. R. Radlauer , A. K. Buckley , L. M. Henling , T. Agapie . Bimetallic coordination insertion polymerization of unprotected polar monomers:copolymerization of amino olefins and ethylene by dinickel bisphenoxyiminato catalysts . J. Am. Chem. Soc. , 2013 . 135 ( 10 ): 3784 - 3787 . DOI: 10.1021/ja4004816 http://doi.org/10.1021/ja4004816 .

J. Wang , H. Li , N. Guo , L. Li , C. L. Stern , T. J. Marks . Covalently linked heterobimetallic catalysts for olefin polymerization . Organometallics , 2004 . 23 ( 22 ): 5112 - 5114 . DOI: 10.1021/om049481b http://doi.org/10.1021/om049481b .

J. Kuwabara , D. Takeuchi , K. Osakada . Zr/Zr and Zr/Fe dinuclear complexes with flexible bridging ligands. Preparation by olefin metathesis reaction of the mononuclear precursors and properties as polymerization catalysts . Organometallics , 2005 . 24 ( 11 ): 2705 - 2712 . .

J. Cano Sierra , D. Hüerländer , M. Hill , G. Kehr , G. Erker , R. Fröhlich . Formation of dinuclear titanium and zirconium complexes by olefin metathesis-catalytic preparation of organometallic catalyst systems . Chem. Eur. J. , 2003 . 9 ( 15 ): 3618 - 3622 . DOI: 10.1002/chem.200304789 http://doi.org/10.1002/chem.200304789 .

Z. Chen , X. Zhao , X. Gong , D. Xu , Y. Ma . Macrocyclic trinuclear nickel phenoxyimine catalysts for high-temperature polymerization of ethylene and isospecific polymerization of propylene . Macromolecules , 2017 . 50 ( 17 ): 6561 - 6568 . DOI: 10.1021/acs.macromol.7b00996 http://doi.org/10.1021/acs.macromol.7b00996 .

P. Wehrmann , S. Mecking . Highly active binuclear neutral nickel(Ⅱ) catalysts affording high molecular weight polyethylene . Organometallics , 2008 . 27 ( 7 ): 1399 - 1408 . DOI: 10.1021/om700942z http://doi.org/10.1021/om700942z .

D. Takeuchi , Y. Chiba , S. Takano , K. Osakada . Double-decker-type dinuclear nickel catalyst for olefin polymerization:efficient incorporation of functional co-monomers . Angew. Chem. Int. Ed. , 2013 . 52 ( 48 ): 12536 - 12540 . DOI: 10.1002/anie.201307741 http://doi.org/10.1002/anie.201307741 .

C. Wang , S. Friedrich , T. R. Younkin , R. T. Li , R. H. Grubbs , D. A. Bansleben , M. W. Day . Neutral nickel(Ⅱ)-based catalysts for ethylene polymerization . Organometallics , 1998 . 17 ( 15 ): 3149 - 3151 . DOI: 10.1021/om980176y http://doi.org/10.1021/om980176y .

E. F. Connor , T. R. Younkin , J. I. Henderson , A. W. Waltman , R. H. Grubbs . Synthesis of neutral nickel catalysts for ethylene polymerization-the influence of ligand size on catalyst stability . Chem. Commun. , 2003 . 18 2272 - 2273 . https://core.ac.uk/download/pdf/4891953.pdf https://core.ac.uk/download/pdf/4891953.pdf , .

M. Delferro , J. P. McInnis , T. J. Marks . Ethylene polymerization characteristics of an electron-deficient nickel(Ⅱ) phenoxyiminato catalyst modulated by non-innocent intramolecular hydrogen bonding . Organometallics , 2010 . 29 ( 21 ): 5040 - 5049 . DOI: 10.1021/om100251j http://doi.org/10.1021/om100251j .

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